CN111040842A - Diesel engine oil composition and preparation method thereof - Google Patents

Diesel engine oil composition and preparation method thereof Download PDF

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CN111040842A
CN111040842A CN201811195381.8A CN201811195381A CN111040842A CN 111040842 A CN111040842 A CN 111040842A CN 201811195381 A CN201811195381 A CN 201811195381A CN 111040842 A CN111040842 A CN 111040842A
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刘依农
徐冰
苏朔
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a diesel engine oil composition and a preparation method thereof. The diesel engine oil composition comprises a viscosity index improver, a detergent, a dispersant, an antioxidant, an antiwear agent, a pour point depressant and a main amount of lubricating base oil; the structure of the viscosity index improver is shown as a general formula (I):

Description

Diesel engine oil composition and preparation method thereof
Technical Field
The invention relates to a lubricating oil composition, in particular to a diesel engine oil composition.
Background
At present, the diesel engine adopts the technologies of direct injection, fuel delayed injection, high top ring piston and tail gas circulation to meet the requirements of high power and low emission, thus causing high working temperature of oil products, large soot content and higher requirements on oil product formulas. For example, in a diesel engine, the working temperature of a piston top bank can reach more than 300 ℃ at most, and the temperature can aggravate oil oxidation to generate a large amount of polar substances such as coking precursors, organic acids, inorganic acids and the like; the existence of soot also brings the problems of oil filter blockage and cylinder sleeve piston ring and valve group abrasion. Thus, the soot dispersion requirements for engine oils are also stringent, e.g., 4.8% soot in CI-4 oils when passing the T-8 bench test. Therefore, the cleaning, dispersing, antioxidant and antiwear abilities of common oil products can not meet the above requirements.
In solving the problem of high-temperature detergency of diesel engine oils, various detergent combinations are often used, for example, a combination of a high base number sulfonate and a high base number sulfurized alkylphenate. In order to solve the problem of soot dispersibility, an ashless dispersant with better dispersibility or a viscosity index improver with dispersibility is required to meet the requirement, but the currently adopted ashless dispersant cannot completely meet the requirement of soot dispersibility, and the dosage needs to be increased, so that the cost of the composition is increased. If the dispersion type tackifier is adopted, the addition amount of the ashless agent can be reduced on the premise of ensuring the dispersion and the wear resistance of oil products to be unchanged, and the cost is reduced, so the dispersant type tackifier is a current research hotspot and has a plurality of related research reports.
CN 1523090A introduces an engine lubricating oil composition, in particular to a lubricating oil composition for a heavy-duty diesel engine, which is characterized in that the lubricating oil composition contains a large amount of hydrogenated base oil, a proper amount of high-base-number salicylate, low-base-number salicylate, sulfurized alkylphenol salt, boronized bissuccinimide ashless dispersant, high-molecular ashless dispersant, zinc dialkyl dithiophosphate and phenol type and amine type auxiliary antioxidant. The lubricating oil composition can meet the specification requirements of SAE J300 and APICF-4 diesel engine oil.
CN 101935574A introduces an engine lubricating oil composition, in particular to a lubricating oil composition for a heavy-duty diesel engine, which is characterized in that the lubricating oil composition contains a large amount of hydrogenated base oil, a proper amount of alkyl salicylate, sulfurized alkyl phenate, sulfonate, a high-molecular ashless dispersant, a polyisobutylene bis (succinimide) ashless dispersant, zinc dialkyl dithiophosphate, a phenol antioxidant, an amine antioxidant and a sulfur-containing antioxidant antiwear agent. The lubricating oil composition can meet the specification requirements of CF-4 diesel engine oil specified in GB 11122-2006.
CN 1782049A relates to a lubricating oil additive composition, which comprises a high molecular weight polyisobutylene succinimide ashless dispersant, a boronized polyisobutylene succinimide dispersant, a polyisobutylene succinimide dispersant coupled with phenol, a metal detergent and an oxidation and corrosion inhibitor by taking the total weight of the composition as a reference. The composition has excellent soot dispersing performance and endows oil products with good oxidation resistance and corrosion resistance. The high-grade diesel engine oil with CF-4 grade or above can be prepared by adding the high-grade diesel engine oil into I-type and II-type base oil or synthetic base oil with high viscosity index.
US 5719107 uses borated high molecular weight polyisobutylene succinimide to prepare heavy-duty diesel engine oil, and the oil product can reach the requirements of API CF-4 and CG-4.
It is seen from the above patent documents that in order to meet the severe high temperature detergency requirements of diesel engine oils, more metallic detergents are required in lubricating oil compositions, while the soot dispersion problem requires ashless dispersants with better performance. The performance requirements of high-grade diesel engine oils are not fully met by the existing detergents and ashless dispersants, and therefore further improvements are needed in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a diesel engine oil composition and a preparation method thereof.
The diesel engine oil composition comprises a viscosity index improver, a detergent, a dispersant, an antioxidant, an antiwear agent, a pour point depressant and a main amount of lubricating base oil; the structure of the viscosity index improver is shown as a general formula (I):
Figure BDA0001828604630000021
in the general formula (I), x sub-repeating units of the n repeating units are the same as or different from each other, and y sub-repeating units of the n repeating units are the same as or different from each other; each R0Are the same or different from each other and are each independently selected from H, C1～C4Alkyl (preferably H and methyl), C2～C4Alkenyl and a group of formula (II), and at least one R0Selected from the group represented by formula (II); r in x sub-repeating units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in x sub-repeat units2Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); r in y sub-repeat units3Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in y sub-repeat units4Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); each A group in the x and y sub-repeat units, which are the same or different from each other, is independently selected from H, C1～C4Alkyl groups (preferably H and methyl), groups of formula (III-a) and groups of formula (III-b); r of n repeating units5Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups);
Figure BDA0001828604630000031
in the formula (II), R6Each independently selected from H, C1～C4Alkyl, phenyl, C7～C10Alkylphenyl, hydroxyphenyl, aminophenyl (preferably H, methyl and phenyl), and may be selected from, for example, H, methyl, ethyl, propyl, butyl, phenyl, tolyl, ethylphenyl, propylphenyl, p-hydroxyphenyl, m-hydroxyphenyl, o-hydroxyphenyl, p-aminophenyl, m-aminophenyl and o-aminophenyl; m is an integer of 0 to 5 (preferably 0, 1, 2 or 3);
Figure BDA0001828604630000032
in formula (III-a), R' is selected from the group consisting of 3-valent C2～C6Hydrocarbyl (preferably C)2～C4Alkyl or alkenyl);
in the formulae (III-a) and (III-b), R' is selected from H, C1～C4Alkyl, phenyl, C7～C10Alkylphenyl (preferably H, methyl and phenyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer of 0 to 5 (preferably an integer of 1 to 4);
x in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000), and y in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000); n is an integer of 1 to 3000 (preferably an integer of 10 to 1000);
at least one sub-repeat unit in which x is greater than 0 or y is greater than 0 is present in one repeat unit of the n repeat units, and at least one A group is selected from the group consisting of a group represented by formula (III-a) and a group represented by formula (III-b).
According to the invention, the weight average molecular weight of the viscosity index improver is 10000-700000, preferably 50000-700000, and more preferably 80000-300000.
According to the invention, the viscosity index improver is a polymer, the main chain of which is preferably a polyolefin, and the polyolefin can be a single C2～20Polymers of olefins, which may also be C2～20Copolymers of two or more (e.g., 3, 4, or 5) of the olefins. The polyolefin is preferably C2～20Copolymers of two of the olefins, most preferably ethylene propylene (preferably, ethylene content of 20% to 80% (more preferably 30% to 70%), propylene content of 20% to 80% (more preferably 40% to 70%).
According to the present invention, the method for preparing the viscosity index improver comprises:
(1) the polyolefin is subjected to oxidative degradation reaction to obtain an oxidative degradation product of the polyolefin;
(2) a step of reacting the product of step (1) with a compound represented by formula (II');
Figure BDA0001828604630000041
in the formula (II'), R6Each independently selected from H, C1～C4Alkyl, phenyl, C7～C10Alkylphenyl, hydroxyphenyl, aminophenyl (preferably H, methyl and phenyl), m is an integer of 0 to 5 (preferably 0, 1, 2 or 3); x is selected from H, F, Cl, Br and I (preferably H, Cl, Br);
(3) a step of reacting the product of the step (2) with a compound represented by the formula (III '-a'), (III '-b') and/or (III '-c');
Figure BDA0001828604630000042
wherein R' is selected from the group consisting of C having a valence of 32～C6Alkyl (preferably C)2～C4Alkyl groups); r' is selected from H, C1～C4Alkyl (preferably H and methyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer of 0 to 5 (preferably an integer of 1 to 4).
According to the method for preparing the viscosity index improver, the polyolefin can be single C2～20Polymers of olefins, which may also be C2～20Copolymers of two or more (e.g., 3, 4, or 5) of the olefins. The polyolefin is preferably C2～20Copolymers of two of the olefins, most preferably BCopolymers of propylene (preferably, ethylene content of 20% to 80% (more preferably 30% to 70%) and propylene content of 20% to 80% (more preferably 40% to 70%).
According to the method for preparing the viscosity index improver, the polyolefin has a structure shown in a general formula (I'):
Figure BDA0001828604630000051
in formula (I'), x sub-repeating units of the n repeating units are the same or different from each other, and y sub-repeating units of the n repeating units are the same or different from each other; each R0Are the same or different from each other and are each independently selected from H, C1～C4Alkyl (preferably H and methyl), C2～C4An alkenyl group; r in x sub-repeating units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in x sub-repeat units2Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); r in y sub-repeat units3Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in y sub-repeat units4Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); each A' group in the x and y sub-repeat units, which are the same or different from each other, is independently selected from H, C1～C4Alkyl (preferably H and methyl); r of n repeating units5Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups);
x in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000), and y in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000); n is an integer of 1 to 3000 (preferably an integer of 10 to 1000); at least one of the repeating units of the n repeating units has a sub-repeating unit in which x is greater than 0 or y is greater than 0, and at least one of the A' groups is selected from H.
According to the preparation method of the viscosity index improver, the weight average molecular weight of the polyolefin is preferably 10000-700000, preferably 50000-700000, and more preferably 80000-300000.
According to the method for preparing a viscosity index improver of the present invention, preferably, the compound represented by the formula (II') may be NH3、C1～C4Alkylamine, aniline, C7～C10Alkyl aniline, diphenylamine, hydroxy aniline and amino aniline, and specifically NH can be selected3One or more of aniline, diphenylamine, p-hydroxyaniline and p-aminoaniline.
According to the method for preparing the viscosity index improver of the present invention, the compound represented by the general formula (III '-a') may be C4～8Alkyl or alkenyl anhydrides, preferably C4～6The alkyl or alkenyl anhydride may be one or more selected from maleic anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride and octanoic anhydride.
According to the preparation method of the viscosity index improver, the compound shown in the general formula (III '-b') can be selected from C2～30Polyene polyamines, preferably C2～10The polyene polyamine can be one or more selected from hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
According to the method for preparing the viscosity index improver, preferably, in the step (1), the polyolefin is dissolved in the lubricating base oil in advance, and the lubricating base oil can be selected from one or more of API I, II, III and IV lubricating base oils, preferably API I and II oils. The I-type oil is lubricating base oil obtained by performing clay refining and solvent refining on distillate oil, the viscosity index of the I-type oil is 80-100, and the kinematic viscosity of the I-type oil at 100 ℃ is 2-10 mm2Between/s; the said class II oil is distillate oilThe viscosity index of the lubricating base oil obtained by hydrotreating is between 100 and 120, and the kinematic viscosity at 100 ℃ is between 2 and 10mm2Between/s; the III-type oil is lubricating base oil obtained by hydrogenating and isomerizing distillate oil, the viscosity index of the III-type oil is more than 120, and the kinematic viscosity of the III-type oil at 100 ℃ is 2-10 mm2The IV oil is α -olefin polymerized synthetic oil, the viscosity index is 120-150, and the kinematic viscosity at 100 ℃ is 2-10 mm2Is between/s. The mass ratio of the polyolefin to the lubricating base oil is 1: 5 to 50 (preferably 1: 8 to 20).
According to the preparation method of the viscosity index improver, the polyolefin is preferably dissolved in the lubricating base oil at 80-250 ℃ (preferably 120-200 ℃), and the dissolving time is preferably 1-20 hours (more preferably 2-10 hours); preferably, an inert gas (preferably nitrogen) is introduced during the dissolution.
According to the preparation method of the viscosity index improver, preferably, in the step (1), the polyolefin and the oxidant are subjected to oxidative degradation reaction in the presence of the catalyst; the oxidant may be oxygen, air, hydrogen peroxide (preferably oxygen or air); the catalyst is preferably selected from porphyrin metal compounds, wherein the metal is preferably selected from one or more of iron, manganese, nickel and magnesium; the catalyst may be selected from phenyl porphyrin metal compounds, tetraphenyl porphyrin metal compounds, tetra (pentafluorophenyl) porphyrin metal compounds (more preferably from tetraphenyl porphyrin metal compounds), and for example, iron phenyl porphyrin, manganese phenyl porphyrin, nickel phenyl porphyrin, magnesium phenyl porphyrin, iron tetraphenyl porphyrin chloride, manganese tetraphenyl porphyrin, nickel tetraphenyl porphyrin, magnesium tetraphenyl porphyrin, iron tetrakis (pentafluorophenyl) porphyrin chloride, manganese tetrakis (pentafluorophenyl) porphyrin, nickel tetrakis (pentafluorophenyl) porphyrin and magnesium tetrakis (pentafluorophenyl) porphyrin (preferably selected from iron tetraphenyl porphyrin chloride, iron tetrakis (pentafluorophenyl) porphyrin chloride) may be used. The catalyst is preferably dissolved in a nitrile solvent selected from the group consisting of acetonitrile, acetonitrile
Figure BDA0001828604630000073
. The mass of the nitrile solvent is preferably 10-10000 times of that of the catalyst.
According to the preparation method of the viscosity index improver, preferably, in the step (1), the tetraphenylporphyrin is obtained by performing a synthetic reaction of benzaldehyde and pyrrole in a solvent, wherein the solvent can be C1～6The fatty acid, sulfone, sulfoxide of (b) may be, for example, propionic acid and/or dimethyl sulfoxide. The preparation method of the tetraphenylporphyrin ferric chloride comprises the steps of mixing tetraphenylporphyrin and FeCl2Reacting and then adding Fe2+Oxidation to Fe3+And the reaction formula is shown as follows:
Figure BDA0001828604630000071
according to the preparation method of the viscosity index improver, the tetra (pentafluorophenyl) porphyrin is obtained by the synthetic reaction of pentafluorobenzaldehyde and pyrrole in a solvent, and the solvent can be C1～6The fatty acid, sulfone, sulfoxide of (b) may be, for example, propionic acid and/or dimethyl sulfoxide. The preparation method of the iron chloride of the tetra (pentafluorophenyl) porphyrin comprises the steps of mixing the tetra (pentafluorophenyl) porphyrin with FeCl2Reacting and then adding Fe2+Oxidation to Fe3+And obtaining the compound. The structure of the iron tetrakis (pentafluorophenyl) porphyrin chloride is as follows:
Figure BDA0001828604630000072
according to the preparation method of the viscosity index improver, preferably, in the step (1), the mass ratio between the polyolefin and the catalyst is 5000-20000: 1 (preferably 6000 to 15000: 1); the temperature of the oxidative degradation reaction is 50-300 ℃ (preferably 100-200 ℃); the pressure of the oxidative degradation reaction is 0.05-2 MPa (preferably 0.1-1 MPa); the time of the oxidative degradation reaction is 1-20 hours (preferably 1-10 hours). After the oxidative degradation reaction in the step (1) is finished, the weight average molecular weight of the oxidative degradation product is preferably 50000-300000 (more preferably 60000-200000), and the acid value is preferably 0.01-6 mgKOH/g (more preferably 0.01-1 mgKOH/g).
According to the method for producing a viscosity index improver of the present invention, preferably, in the step (1), the catalyst is separated from the oxidative degradation product. The separation method includes distillation, extraction and the like, and is not particularly limited.
According to the preparation method of the viscosity index improver, when the porphyrin metal compound is adopted to catalyze, oxidize and degrade, the obtained oxidation degradation product has a relatively regular molecular structure, and the thickening capacity and the shearing stability of the oxidation degradation product are superior to those of other polyolefins obtained by mechanical degradation, thermal degradation and metal catalyst catalytic oxidation degradation.
According to the method for preparing the viscosity index improver, preferably, in the step (2), the molar ratio of the product of the step (1) to the compound represented by the formula (II') is 1: 0.5 to 10 (preferably 1:1 to 5). The reaction temperature in the step (2) is 80-200 ℃ (preferably 100-150 ℃); the reaction time of the step (2) is 0.5-5 h (preferably 1-3 h).
According to the method for preparing the viscosity index improver of the present invention, preferably, in the step (3), the reaction with the compound represented by the formula (III '-a'), (III '-b') and/or the compound represented by the formula (III '-c') is a reaction with the compound represented by the formula (III '-a'), (III '-b'), a reaction with the compound represented by the formula (III '-c'), or a reaction with a mixture of the compounds represented by the formula (III '-a'), (III '-b'), (III '-c'). The reaction with the compounds represented by the formulae (III '-a') and (III '-b') means that the reaction with the compound represented by the formula (III '-a') may be carried out first and then with the compound represented by the formula (III '-b').
According to the preparation method of the viscosity index improver, preferably, in the step (3), the molar ratio of the product of the step (2) to the compound represented by the formula (III '-a') or the compound represented by the formula (III '-b') is 1: 100-500: 100-500, preferably 1: 150-350: 150 to 350 parts by weight; the molar ratio between the polyolefin and the compound of formula (III '-c') is 1: 100-500, preferably 1: 150 to 350.
According to the method for preparing the viscosity index improver, preferably, in the step (3), when the product of the step (2) is reacted with the compounds represented by the formulas (III '-a'), (III '-b'), the product of the step (2) is reacted with the compound represented by the formula (III '-a') first and then with the compound represented by the formula (III '-b'). The reaction temperature of the product in the step (2) and the compound shown in the formula (III '-a') is 100-200 ℃ (preferably 140-180 ℃), and the reaction time is 1-5 hours (preferably 2-4 hours). The reaction temperature of the reaction product of the product in the step (2) and the compound shown in the formula (III '-a') and the compound shown in the formula (III '-b') is 50-200 ℃ (preferably 80-120 ℃), and the reaction time is 1-10 hours (preferably 2-4 hours).
According to the preparation method of the viscosity index improver, preferably, in the step (3), when the product of the step (2) reacts with the compound represented by the formula (III '-c'), the reaction temperature is preferably 50-200 ℃ (preferably 80-120 ℃), and the reaction time is preferably 1-10 hours (preferably 2-4 hours).
According to the method for preparing the viscosity index improver of the present invention, it is preferable that an initiator is added in the reaction of the step (3). The initiator is preferably an azo compound and/or a peroxide, and for example, one or more of azobisbutyronitrile, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyrocarboxamide, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyvalerate and methyl ethyl ketone peroxide (preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, di-t-butyl peroxide and dicumyl peroxide) may be used. The addition amount of the initiator is preferably 1-50% of the polyolefin, and preferably 5-25%.
According to the method for preparing the viscosity index improver, inert gas (preferably nitrogen gas) is preferably introduced into the reactions in the steps (1), (2) and (3).
According to the method for preparing the viscosity index improver of the present invention, after the reaction in the step (1) and the step (2) is completed, the reaction product may be purified, or the reaction in the next step may be directly performed, and is not particularly limited. The purification treatment method includes one or more of filtration, centrifugation, water washing, distillation, drying and recrystallization methods, and is not particularly limited. After the reaction in step (3) is completed, the reaction product is preferably subjected to a purification treatment, which includes one or more of filtration, centrifugation, water washing, distillation, drying and recrystallization, and is not particularly limited.
According to the preparation method of the viscosity index improver, preferably, when the polyolefin is dissolved in the lubricating base oil, a certain amount of lubricating base oil is contained in a final reaction product, and the lubricating base oil can be separated or not separated, so that the technical effect of the invention is not influenced; when the reaction product is applied to a lubricating oil, it is more unnecessary to separate the lubricating base oil from the reaction product.
According to the invention, the viscosity index improver has good detergency, dispersibility, antioxidant property and antiwear property, can reduce the dosage of ashless dispersant and antiwear agent, and can be used for improving the viscosity-temperature properties of gasoline engine oil and diesel engine oil.
According to the diesel engine oil composition, the detergent is selected from one or more of sulfonate, sulfurized alkylphenol salt and alkylphenol salt, preferably a mixture of sulfonate and sulfurized alkylphenol salt, and the mass ratio of the sulfonate to the sulfurized alkylphenol salt is 5-1: 1 to 2. The sulfonate is preferably calcium sulfonate, more preferably a mixture of high-base-number calcium sulfonate and low-base-number calcium sulfonate, and the mass ratio of the high-base-number calcium sulfonate to the low-base-number calcium sulfonate is 4-1: 1 to 1. The high base number calcium sulfonate is preferably calcium sulfonate with a base number of 200mgKOH/g or more. The low-base-number calcium sulfonate is preferably calcium sulfonate with a base number of 20-50 mgKOH/g. The sulfurized alkylphenol salt is preferably an overbased sulfurized alkylphenol salt with a base number of more than 200mgKOH/g, and can be one or more of sulfurized calcium alkyl phenate, sulfurized magnesium alkyl phenate and sulfurized calcium magnesium alkyl phenate composite salt, and more preferably, the overbased sulfurized calcium alkyl phenate composite salt and/or the overbased sulfurized calcium alkyl phenate with a base number of more than 200 mgKOH/g.
According to the diesel engine oil composition, the dispersant is preferably polyisobutylene succinimide ashless dispersant, more preferably a mixture of polyisobutylene mono-succinimide and polyisobutylene di-succinimide, the mass ratio of the polyisobutylene mono-succinimide and the polyisobutylene di-succinimide is 1: 1-6, and the commercial brands include T151 and T152.
According to the diesel engine oil composition, the antioxidant is preferably dialkyl zinc dithiophosphate and/or an ashless antioxidant, more preferably a mixture of dialkyl zinc dithiophosphate and the ashless antioxidant, the mass ratio of the dialkyl zinc dithiophosphate to the ashless antioxidant is 1: 0.1-10, the ashless antioxidant is preferably one or more of an aromatic amine antioxidant, a phenolic ester antioxidant and a shielding phenolic antioxidant, the aromatic amine antioxidant can be dialkyl diphenylamine, the phenolic ester antioxidant can be β - (3, 5-di-tert-butyl-4-hydroxyphenyl) octyl propionate, and the shielding phenolic antioxidant can be 2, 6-di-tert-butyl-p-cresol.
According to the diesel engine oil composition of the invention, the antiwear agent is preferably one or more of phosphate, phosphite and thiocarbamate, for example, tricresyl phosphate, phosphite, dialkyl dithiocarbamate can be selected, and common trade marks include T306, T304, T323.
According to the diesel engine oil composition of the present invention, the pour point depressant is preferably one or more of poly α -olefin, polyfumarate and polymethacrylate, preferably poly α -olefin pour point depressant, common commercial designations include T803, T803B.
According to the diesel engine oil composition, the lubricating base oil is preferably one or more selected from API I, II, III, IV and V base oils, and the viscosity at 100 ℃ is more preferably 1-40 mm2(more preferably 4 to 35 mm)2S) lubricating base oil.
According to the diesel engine oil composition, the viscosity index improver accounts for 1-15%, preferably 2-10% of the total mass of the composition; the detergent accounts for 1-12% of the total mass of the composition, and preferably 2-10%; the dispersant accounts for 1 to 15 percent of the total mass of the composition, preferably 2 to 10 percent; the antioxidant accounts for 0.05-6%, preferably 1-3% of the total mass of the composition; the antiwear agent accounts for 0.05-3%, preferably 0.1-1% of the total mass of the composition; the pour point depressant accounts for 0.05 to 3 percent of the total mass of the composition, preferably 0.1 to 1 percent; the lubricating base oil constitutes the main component of the composition.
The preparation method of the diesel engine oil composition comprises the step of mixing various additives and lubricating base oil.
The diesel engine oil composition has excellent high-temperature detergency, soot dispersibility, oxidation resistance, abrasion resistance, metal corrosion inhibition performance and low-temperature performance, can meet the requirement of API CI-4 specification, and has reduced phosphorus content and can meet the requirement of environmental emission.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, steps, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently used, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
In the context of the present invention, the expression "halo" refers to fluoro, chloro, bromo or iodo.
In the context of the present invention, the term "hydrocarbyl" has the meaning conventionally known in the art and includes straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, or combinations thereof, wherein straight or branched chain alkyl, straight or branched chain alkenyl, cycloalkyl, cycloalkenyl, aryl, or combinations thereof are preferred. Specific examples of the hydrocarbon group include C1-50A hydrocarbon radical comprising C1-50Straight or branched alkyl, C2-50Straight-chain or branched alkenyl, C2-50Straight-chain or branched alkynyl, C3-50Cycloalkyl radical, C3-50Cycloalkenyl radical, C3-50Cycloalkynyl group, C6-50Aryl or a combination thereof, wherein C is preferred1-50Straight or branched alkyl, C2-50Straight-chain or branched alkenyl, C3-50Cycloalkyl radical, C3-50Cycloalkenyl radical, C6-50Aryl or a combination thereof. The combined group includes a group obtained by bonding or substitution of one or more groups selected from a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, and an aryl group. By bonded is meant that one group forms a chemical bond (preferably a covalent bond) with one or more other groups. The substitution refers to one group as a substituent to replace a hydrogen atom in another group. As said combinationRadicals such as may be mentioned of one or more C1-50Straight or branched chain alkyl (preferably one or more C)1-20Straight or branched alkyl) with one or more C6-50Radicals obtained by bonding or substitution of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C1-50Straight or branched alkenyl (preferably one or more C)1-20Straight or branched alkenyl) with one or more C6-50Radicals obtained by bonding or substitution of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C1-50Straight or branched chain alkyl (preferably one or more C)1-20Straight or branched alkyl) with one or more C3-50A group obtained by bonding or substitution of a cycloalkyl group (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl groups), one or more C1-50Straight or branched alkenyl (preferably one or more C)1-20Straight or branched alkenyl) with one or more C3-50A group obtained by bonding or substitution of a cycloalkyl group (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl groups), one or more C1-50Straight or branched chain alkyl (preferably one or more C)1-20Straight or branched alkyl) with one or more C3-50A group obtained by bonding or substitution of cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl), one or more C1-50Straight or branched alkenyl (preferably one or more C)1-20Straight or branched alkenyl) with one or more C3-50Cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl) groups obtained by bonding or substitution. As the above-mentioned combination group, there may be mentioned, for example, one or more C1-50Straight or branched alkylphenyl, mono-or polyphenyl C1-50Straight or branched chain alkyl or mono-or poly-C1-50C bonded by straight-chain or branched alkylphenyl radicals1-50Straight or branched chain alkyl, etc., of which C is more preferable1-50Straight or branched alkylphenyl radicals, e.g. tert-butylphenyl, phenyl C1-50Straight or branched alkyl (e.g. benzyl) or C1-50C bonded by straight-chain or branched alkylphenyl radicals1-50Straight or branched chain alkyl (such as t-butylbenzyl).
In the context of the present invention, by "heterohydrocarbyl" is meant one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH within the hydrocarbyl molecular structure (excluding the end of the backbone or any side chain in the hydrocarbyl molecular structure)2The radicals-being selected from-O-, -S-, -N ═ N-and-NR '- (R' is H or C1-4Straight or branched chain alkyl), or one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH inside the hydrocarbon-based molecular structure (excluding the end of the main chain or any side chain in the hydrocarbon-based molecular structure)<Radical substituted by radical-N<A group obtained by direct substitution. Obviously, from the viewpoint of structural stability, when a plurality of substituent groups are present, the substituent groups are not directly bonded to each other; and only when a plurality of-S-S-S are present, these-S-S may be directly bonded to each other. As said substituent, it is preferably-O-or-S-. The number of carbon atoms of the hydrocarbon group is represented by the group-CH2-or a group-CH<Substituted with a corresponding decrease, but for the sake of simplicity, the number of carbon atoms of the hydrocarbon group before the substitution is still used to refer to the number of carbon atoms of the heterohydrocarbon group. By "heteroalkyl" is meant a straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heteroalkynyl, straight or branched heterocyclyl, straight or branched heterocyclenyl, straight or branched heterocycloalkynyl, straight or branched heteroaryl, or combinations thereof, with straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heterocyclyl, straight or branched heterocycloalkenyl, straight or branched heteroaryl, or combinations thereof being preferred. As the heterohydrocarbon group, a linear or branched heteroalkyl group is exemplified, C4Straight chain alkyl radicals such as
Figure BDA0001828604630000131
(the group indicated by the arrow in the formula is not located within the molecular structure but at the end of the main chain) direct substitution with a substituent-O-will give-CH2-O-CH2-CH3or-CH2-CH2-O-CH3Is called C4A linear heteroalkyl group. Or, C4Branched alkyl radicals such as
Figure BDA0001828604630000132
(the groups indicated by the arrows are not located within the molecular structure but at the ends of the main and side chains) by a substituent-N<Direct substitution will result in
Figure BDA0001828604630000141
Is called C4A branched heteroalkyl group. According to the invention, as the heterohydrocarbyl group, there may be mentioned, for example, C3-50Heterohydrocarbyl, of which C is preferred3-20Straight or branched heteroalkyl radicals or C3-6Linear or branched heteroalkyl.
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).
In the context of the present specification, a hydrocarbyl or heterohydrocarbyl group or the like substituted with a substituent group refers to a hydrocarbyl or heterohydrocarbyl group that is obtained by substituting a hydrogen atom in the hydrocarbyl or heterohydrocarbyl group with the substituent group. The substituent group is preferably selected from C1-20Alkoxy, hydroxy, amino and mercapto.
In the context of the present specification, a hydrocarbyl or heterohydrocarbyl group or the like substituted with one or more substituent groups refers to a hydrocarbyl or heterohydrocarbyl group that is obtained by substituting a hydrogen atom in the hydrocarbyl or heterohydrocarbyl group with one or more substituent groups.
In the context of the present specification, a hydrocarbyl or heterohydrocarbyl group or the like optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) substituent groups refers to a hydrocarbyl or heterohydrocarbyl group optionally substituted with one or more substituent groups for the hydrogen atoms in the hydrocarbyl or heterohydrocarbyl group, and may also optionally be substituted with unsubstituted groups.
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
The method for measuring the weight average molecular weight adopted by the invention is gel permeation chromatography, and the model of a Gel Permeation Chromatograph (GPC) is Waters1515, United states Waters company; testing parameters: 7725 hand sample injector, 1515 isocratic pump, 2414 refractive index detector; the Waters STYRAGEL chromatographic columns are connected in series by 4 types: HR0.5+ HR1+ HR 2; mobile phase: tetrahydrofuran; flow time: 1 mL/min; and (3) testing temperature: at 40 ℃.
The performance evaluation method employed in the embodiment is as follows:
high-temperature detergency:
paint formation and coke-forming panel experiments were performed on an L-1 type panel coke former. Coke formation: the plate temperature/oil temperature is 320 ℃/100 ℃, the time is 2 hours, and the stop/start time is 45 seconds/15 seconds. Forming paint: the temperature of the plate/oil is 300 ℃/150 ℃ and the time is 2 hours, and the process is continuous.
The test was conducted on an L-A type detergency tester to examine the high-temperature detergency thereof. The temperature of the plate/oil is 300 ℃/100 ℃, the time is 1 hour, and the stop/start time is 40 seconds/20 seconds. The oil drop velocity was 1.0 ml/min.
Antioxidant stability:
the thermal oxidation stability of the oil product is examined by a PDSC pressure differential scanning calorimetry method.
Dispersibility test:
dispersing 2.5% carbon black in oil, stirring at high speed, keeping the temperature at 50 deg.C for 18h, dripping oil, and calculating the ratio of diffusion ring to oil ring.
Oil film breaking load: an antifriction and antiwear performance evaluation method of GB/T3142-82 lubricant.
The diameter of the abrasion marks: SH/T0189 lubricating oil antiwear performance test method (four-ball method).
And (3) corrosion resistance test: ASTM D5968(CBT) method for evaluating metal corrosion.
The names and indices of the main additives used are as follows:
high base number calcium sulfonate T106: the base number is 311mgKOH/g, the calcium content is 10.2 percent, the sulfur content is 1.8 percent, and the Liaoning Tianhe fine chemical industry Co., Ltd; low base number calcium sulfonate T104: base number 28mgKOH/g, calcium content 1.5%, sulfur content 2%, available from southern additive company without tin; high base number sulfurized calcium alkyl phenate T122 with base number of 260mgKOH/g, calcium content of 10.9%, sulfur content of 3.0%, available from southern additive company without tin;
monomeric polyisobutylene succinimide (T151) with a nitrogen content of 2.1% and a base number of 50mgKOH/g, produced by southern additive company without tin; diisobutylene succinimide (T152), nitrogen content 1.25%, base number 55mgKOH/g, produced by southern additive company without tin;
zinc dialkyl dithiophosphate (T203) with 10.2 percent of zinc, 14.0 percent of sulfur and 7.7 percent of phosphorus, which is produced by Liaoning Nintendo Fine chemical Co., Ltd;
dialkyl diphenylamine (T534) with nitrogen content of 4.6 percent and base number of 179mgKOH/g, produced by Liaoning Tianhe Fine chemical Co., Ltd; t512 phenolic ester type antioxidant, flash point (open), 224 ℃, density (20 ℃), 0.9628g/cm3Manufactured by Beijing Xinpu fine chemical Co., Ltd;
tricresyl phosphate (T306), acid value less than or equal to 0.10mgKOH/g, specific gravity less than or equal to 1.185, Zibo Whiteflower chemical Co., Ltd; dialkyl dithio-amino formate (T323), flash point greater than 170 deg.C, Liaoning Tianhe fine chemical industry Co., Ltd; phosphite ester (T304), the phosphorus content is 14.5% -16.0%, the acid value is less than or equal to 15mgKOH/g, Zibo Whitney chemical company Limited;
the dispersed viscosity index improver DOCP of the foreign ethylene-propylene copolymer has the following nitrogen content: 0.25% and a weight average molecular weight Mw of 182500, manufactured by Exxon.
Tetrakis (pentafluorophenyl) phenyl iron chloride porphyrin, purity: 95% or more, by the company welfare; iron tetraphenylporphyrin chloride, purity: 95% or more, Bailingwei Co.
EXAMPLE 1 preparation of DOCP-1, a Dispersion-type ethylene-propylene copolymer viscosity index improver
A500 ml autoclave equipped with temperature control, water cooling and stirring was charged with 10 g of an ethylene-propylene copolymer (Mw: 182000, (0.000055mol) having an ethylene content of 58% and available from Jilin petrochemical company, China) and cut into 0.5cm pieces3Then 90 g of 150SN (manufactured by china petrochemical high-bridge oil company), 1.137 mg (0.001mol) of tetrakis (pentafluorophenyl) phenylferriporphyrin chloride (M ═ 1136.7) (dissolved in 2 g of acetonitrile), after addition, the temperature was raised to 100 ℃ and air was introduced, the reaction pressure was maintained at 0.2MPa, the oxidation reaction was stopped after 6 hours of constant temperature reaction, the catalyst was separated by filtration, and a mixture of the oxidative degradation product of the copolymer and 150SN was obtained, wherein the weight average molecular weight of the oxidative degradation product was 105200 and the acid value was 0.11 mgKOH/g. Adding 0.022 g of p-hydroxyaniline (M ═ 109.13) into a mixture of an oxidative degradation product of a copolymer and 150SN, controlling the reaction temperature at 130 ℃, reacting for 2 hours, heating the materials to 150 ℃ under the protection of nitrogen, adding 1.2 g of azobisbutyronitrile and 2.3 g (0.024mol) of maleic anhydride, dropwise adding 2.48 g (0.024mol) of diethylenetriamine after reacting for 2 hours, reacting for 2 hours at 100 ℃, and introducing nitrogen for purging after the reaction to obtain a product DOCP-1, wherein the nitrogen content is 0.21%.
EXAMPLE 2 preparation of DOCP-2, a Dispersion-type ethylene-propylene copolymer viscosity index improver
With temperature control and water cooling10 g of an ethylene-propylene copolymer (Mw: 182000, ethylene content 58%, available from Jilin petrochemical Co., Ltd., China) was charged into a 500-ml stirred autoclave, and the mixture was cut into 0.5cm pieces3Then 90 g of 150SN (produced by China petrochemical high-bridge oil Co.), 0.7 mg of tetraphenylporphyrin ferric chloride (M is 704.02, 0.001mol) (dissolved in 1.5 g of acetonitrile), heating to 110 ℃, introducing air, keeping the reaction pressure at 0.3MPa, keeping the temperature constant for 4 hours, stopping the oxidation reaction, filtering to separate out the catalyst, obtaining a mixture of the oxidative degradation product of the copolymer and 150SN, and measuring the weight average molecular weight of the oxidative degradation product to be 110600 and the acid value to be 0.20 mgKOH/g. Adding 0.034 g of p-diphenylamine (M & gt 169.22) into a mixture of an oxidative degradation product of a copolymer and 150SN, controlling the reaction temperature at 120 ℃, reacting for 2 hours, heating the materials to 150 ℃ under the protection of nitrogen, adding 1.0 g of benzoyl peroxide and 2.0 g (0.020mol) of maleic anhydride, dropwise adding 3.5 g (0.024mol) of triethylene tetramine after reacting for 2 hours, reacting for 2 hours at 103 ℃, and introducing nitrogen for purging after the reaction to obtain a product DOCP-2 with the nitrogen content of 0.22%.
EXAMPLE 3 preparation of DOCP-3 Dispersion-type ethylene-propylene copolymer viscosity index improver
10 g of ethylene-propylene copolymer (Mw: 182000, ethylene content 58%, available from Jilin petrochemical Co., Ltd., China) were placed in a 500-ml autoclave with temperature control, water cooling and stirring, and cut into 0.5cm pieces3Then 90 g of 150SN (manufactured by china petrochemical high-bridge oil company), 1.5 mg (0.0013mol) of tetrakis (pentafluorophenyl) phenylferriporphyrin chloride (M ═ 1136.7) (dissolved in 3 g of acetonitrile), heated to 100 ℃, and air was introduced while maintaining the reaction pressure at 0.4MPa, and the temperature was maintained at constant temperature for 7 hours, the oxidation reaction was stopped, the catalyst was separated by filtration, and a mixture of the oxidative degradation product of the copolymer and 150SN was obtained, wherein the weight average molecular weight of the oxidative degradation product was 123000, and the acid value was 0.15. mgKOH/g. 0.022 g of p-hydroxyaniline (M ═ 109.13) was added thereto, and the reaction temperature was controlled at 120 ℃ for 3 hours. Under the protection of nitrogen, heating the mixture of the oxidative degradation product of the copolymer and 150SN to 150 ℃, adding 1.5 g of azobutyronitrile and 2.0 g (0.020mol) of maleic anhydride,reacting for 1.5 hours, dropwise adding 2.6 g (0.025mol) of diethylenetriamine, reacting for 2 hours at 90 ℃, and introducing nitrogen for purging after the reaction to obtain a product DOCP-3 with the nitrogen content of 0.20%.
EXAMPLE 4 preparation of sulfurized calcium magnesium alkyl phenolate composite salt
Adding 70 g of dodecylphenol and 75 g of 150SN neutral oil into a 500ml three-neck flask which is provided with a temperature control system and is electrically stirred, stirring for 15 minutes, adding 18 g of sulfur, 4 g of calcium oxide and 4 g of magnesium oxide, heating to 90 ℃ to react for 50 minutes, gradually deepening the color of the reaction material, discharging hydrogen sulfide gas, and introducing the reaction tail gas into a 10% sodium hydroxide solution absorption device. Then the temperature was gradually raised to 150 ℃, then 8g of decaol, 4 g of calcium oxide, 4 g of magnesium oxide and 35 g of ethylene glycol were added dropwise over a period of 1 hour. The reaction temperature was controlled at 150 ℃ and the high alkalization reaction was carried out by feeding carbon dioxide, a second addition of 4 g of calcium oxide and 4 g of magnesium oxide was carried out when the carbon dioxide absorption reached 5.85 g (93% of the theoretical 6.29 g), carbon dioxide was fed in, a third addition of 4 g of calcium oxide and 4 g of magnesium oxide was carried out when the carbon dioxide absorption reached 5.97 g (95% of the theoretical 6.29 g), and finally carbon dioxide was fed in until 6.16 g (98% of the theoretical 6.29 g) was reached. Then cooling to 120 ℃, adding 100 g of No. 120 gasoline and 20 g of diatomite filter aid for filtration, carrying out reduced pressure distillation on the high-base number calcium alkylphenol sulfide containing gasoline, controlling the temperature at the bottom of the kettle to 170 ℃, and the vacuum degree to be more than 0.09MPa, distilling out the solvent and ethylene glycol to obtain the high-base number calcium alkylphenol sulfide composite salt, wherein the base number of the high-base number calcium alkylphenol sulfide composite salt is 275mgKOH/g, the sulfur content is 2.3%, the calcium content is 4.9%, the magnesium content is 5.2%, and the kinematic viscosity at 100 ℃ is 157mm2/s。
Examples 5 to 8 of Diesel Engine oil composition and comparative examples 1 to 4
And (3) the 150SN, the 500SN and the 150BS are in accordance with the following 75: 25: 5 to prepare the lubricating base oil, and the performance of the lubricating base oil can meet the requirement of 15W/40 base oil.
According to the formulation composition of Table 1, examples 5 to 8 and comparative examples 1 to 3 of diesel engine oil compositions were prepared, and comparative example 4 was a commercially available 15W/40CI-4 diesel engine oil. The compositions were subjected to evaluation tests for detergency, oxidation resistance, dispersibility, abrasion resistance and metal corrosion, respectively, and the test results are shown in Table 2.
TABLE 1 examples 5 to 8 and comparative examples 1 to 4 of Diesel Engine oil compositions
Figure BDA0001828604630000181
Table 2 evaluation test results
Figure BDA0001828604630000191

Claims (12)

1. A diesel engine oil composition comprising a viscosity index improver, a detergent, a dispersant, an antioxidant, an antiwear agent, a pour point depressant and a major amount of a lubricating base oil; the structure of the viscosity index improver is shown as a general formula (I):
Figure FDA0001828604620000011
in the general formula (I), x sub-repeating units of the n repeating units are the same as or different from each other, and y sub-repeating units of the n repeating units are the same as or different from each other; each R0Are the same or different from each other and are each independently selected from H, C1～C4Alkyl (preferably H and methyl), C2～C4Alkenyl and a group of formula (II), and at least one R0Selected from the group represented by formula (II); r in x sub-repeating units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in x sub-repeat units2Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); r in y sub-repeat units3Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in y sub-repeat units4Are the same or different from each other and are each independently selected from single bondsAnd C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); each A group in the x and y sub-repeat units, which are the same or different from each other, is independently selected from H, C1～C4Alkyl groups (preferably H and methyl), groups of formula (III-a) and groups of formula (III-b); r of n repeating units5Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups);
Figure FDA0001828604620000012
in the formula (II), R6Each independently selected from H, C1～C4Alkyl, phenyl, C7～C10Alkylphenyl, hydroxyphenyl, aminophenyl (preferably H, methyl and phenyl), and may be selected from, for example, H, methyl, ethyl, propyl, butyl, phenyl, tolyl, ethylphenyl, propylphenyl, p-hydroxyphenyl, m-hydroxyphenyl, o-hydroxyphenyl, p-aminophenyl, m-aminophenyl and o-aminophenyl; m is an integer of 0 to 5 (preferably 0, 1, 2 or 3);
Figure FDA0001828604620000021
in formula (III-a), R' is selected from the group consisting of 3-valent C2～C6Hydrocarbyl (preferably C)2～C4Alkyl or alkenyl);
in the formulae (III-a) and (III-b), R' is selected from H, C1～C4Alkyl, phenyl, C7～C10Alkylphenyl (preferably H, methyl and phenyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer of 0 to 5 (preferably an integer of 1 to 4);
x in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000), and y in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000); n is an integer of 1 to 3000 (preferably an integer of 10 to 1000);
at least one sub-repeat unit in which x is greater than 0 or y is greater than 0 is present in one repeat unit of the n repeat units, and at least one A group is selected from the group consisting of a group represented by formula (III-a) and a group represented by formula (III-b).
2. The diesel engine oil composition as claimed in claim 1, wherein the viscosity index improver has a weight average molecular weight of 10000 to 700000 (preferably 80000 to 300000).
3. The diesel oil composition of claim 1, wherein the viscosity index improver is a polymer having a backbone of a polyolefin (the polyolefin is a single C)2～20Polymers of olefins, or being C2～20Copolymers of two or more (e.g., 3, 4, or 5) of the olefins).
4. The diesel engine oil composition of claim 1, wherein the viscosity index improver is prepared by a method comprising:
(1) the polyolefin is subjected to oxidative degradation reaction to obtain an oxidative degradation product of the polyolefin;
(2) a step of reacting the product of step (1) with a compound represented by formula (II');
Figure FDA0001828604620000022
in the formula (II'), R6Each independently selected from H, C1～C4Alkyl, phenyl, C7～C10Alkylphenyl, hydroxyphenyl, aminophenyl (preferably H, methyl and phenyl), m is an integer of 0 to 5 (preferably 0, 1, 2 or 3); x is selected from H, F, Cl, Br and I (preferably H, Cl, Br);
(3) a step of reacting the product of the step (2) with a compound represented by the formula (III '-a'), (III '-b') and/or (III '-c');
Figure FDA0001828604620000031
wherein R' is selected from the group consisting of C having a valence of 32～C6Alkyl (preferably C)2～C4Alkyl groups); r' is selected from H, C1～C4Alkyl (preferably H and methyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer of 0 to 5 (preferably an integer of 1 to 4).
5. The diesel engine oil composition of claim 4 wherein the polyolefin is a single C2～20Polymers of olefins, or being C2～20Copolymers of two or more (e.g., 3, 4, or 5) of the olefins.
6. The diesel engine oil composition of claim 4 wherein the polyolefin is of the formula (I'):
Figure FDA0001828604620000032
in formula (I'), x sub-repeating units of the n repeating units are the same or different from each other, and y sub-repeating units of the n repeating units are the same or different from each other; each R0Are the same or different from each other and are each independently selected from H, C1～C4Alkyl (preferably H and methyl), C2～C4An alkenyl group; r in x sub-repeating units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in x sub-repeat units2Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); r in y sub-repeat units3Are the same or different from each other and are each independently selected from H and C1～C4Alkyl (preferably H and methyl)) R in y sub-repeat units4Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups); each A' group in the x and y sub-repeat units, which are the same or different from each other, is independently selected from H, C1～C4Alkyl (preferably H and methyl); r of n repeating units5Are the same or different from each other and are each independently selected from the group consisting of a single bond and C1～C6Alkylene (preferably selected from single bond and C)1～C4Alkylene groups);
x in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000), and y in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000); n is an integer of 1 to 3000 (preferably an integer of 10 to 1000); at least one of the repeating units of the n repeating units has a sub-repeating unit in which x is greater than 0 or y is greater than 0, and at least one of the A' groups is selected from H.
7. The diesel engine oil composition according to claim 4,
the compound of formula (II') is NH3、C1～C4Alkylamine, aniline, C7～C10Alkyl aniline, diphenylamine, hydroxy aniline, amino aniline (preferably NH)3One or more of aniline, diphenylamine, p-hydroxyaniline and p-aminoaniline);
the compound represented by the general formula (III '-a') is C4～8Alkyl or alkenyl anhydrides (preferably C)4～6Alkyl or alkenyl anhydrides, more preferably one or more of maleic anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, and octanoic anhydride);
the compound represented by the general formula (III '-b') is C2～30Polyene polyamine (preferably C)2～10A polyene polyamine, more preferably one or more of hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine).
8. The diesel engine oil composition according to claim 4,
in step (1), the oxidative degradation reaction is carried out by reacting the polyolefin with an oxidizing agent in the presence of a catalyst; the oxidant is oxygen, air, hydrogen peroxide (preferably oxygen or air); the catalyst is selected from porphyrin metal compounds, wherein the metal is selected from one or more of iron, manganese, nickel and magnesium;
in the step (1), the mass ratio of the polyolefin to the catalyst is 5000-20000: 1 (preferably 6000 to 15000: 1); the temperature of the oxidative degradation reaction is 50-300 ℃ (preferably 100-200 ℃); the pressure of the oxidative degradation reaction is 0.05-2 MPa (preferably 0.1-1 MPa); the time of the oxidative degradation reaction is 1-20 hours (preferably 1-10 hours); in step (2), the molar ratio between the product of step (1) and the compound of formula (II') is 1: 0.5 to 10 (preferably 1:1 to 5); the reaction temperature in the step (2) is 80-200 ℃ (preferably 100-150 ℃); the reaction time of the step (2) is 0.5-5 h (preferably 1-3 h);
in the step (3), the molar ratio of the product of the step (2) to the compound represented by the formula (III '-a') or the compound represented by the formula (III '-b') is 1: 100-500: 100-500 (preferably 1: 150-350); the molar ratio between the polyolefin and the compound of formula (III '-c') is 1: 100-500 (preferably 1: 150-350);
in the step (3), when the product of the step (2) is reacted with the compounds shown in the formulas (III '-a') and (III '-b'), the product of the step (2) is firstly reacted with the compound shown in the formula (III '-a') and then reacted with the compound shown in the formula (III '-b'); the reaction temperature of the product in the step (2) and the compound shown in the formula (III '-a') is 100-200 ℃ (preferably 140-180 ℃), and the reaction time is 1-5 hours (preferably 2-4 hours); the reaction temperature of the reaction product of the product in the step (2) and the compound shown in the formula (III '-a') and the compound shown in the formula (III '-b') is 50-200 ℃ (preferably 80-120 ℃), and the reaction time is 1-10 hours (preferably 3-6 hours).
9. The diesel engine oil composition as claimed in claim 1, wherein the detergent is selected from one or more of sulfonates, sulfurized alkylphenates and alkylphenates (preferably a mixture of sulfonates and sulfurized alkylphenates at a mass ratio of 5-1: 1-2), the dispersant is selected from polyisobutylene succinimide ashless dispersants (preferably a mixture of polyisobutylene monobutyldiimide and polyisobutylene bissuccinimide at a mass ratio of 1: 1-6), the antioxidant is selected from zinc dialkyldithiophosphate and/or ashless antioxidants (preferably a mixture of zinc dialkyldithiophosphate and ashless antioxidants at a mass ratio of 1: 0.1-10), the antiwear agent is preferably one or more of phosphate, phosphite and thiocarbamate, the pour point depressant is selected from one or more of poly α -olefins, polyfumarate and polymethacrylates (preferably poly α -olefin pour point depressant), and the lubricating base oil is selected from one or more of API group I, II, III, IV and V (preferably a viscosity at 100 ℃ of 1-40 mm)2(more preferably 4 to 35 mm)2Lubricating base oil per second)).
10. The diesel engine oil composition as claimed in claim 9, wherein the sulfonate is calcium sulfonate (preferably a mixture of high base number calcium sulfonate and low base number calcium sulfonate, and the mass ratio of the two is 4-1: 1-1); the sulfurized alkylphenol salt is high-base-number sulfurized alkylphenol salt with a base number of more than 200mgKOH/g (preferably high-base-number sulfurized calcium-magnesium alkylphenol composite salt with a base number of more than 200mgKOH/g and/or high-base-number sulfurized calcium alkylphenol).
11. The diesel engine oil composition according to any one of claims 1 to 10, wherein the viscosity index improver comprises 1 to 15% (preferably 2 to 10%) of the total mass of the composition, based on the total mass of the diesel engine oil composition; the detergent accounts for 1-12% (preferably 2-10%) of the total mass of the composition; the dispersant accounts for 1 to 15 percent (preferably 2 to 10 percent) of the total mass of the composition; the antioxidant accounts for 0.05-6% (preferably 1-3%) of the total mass of the composition; the antiwear agent accounts for 0.05-3% (preferably 0.1-1%) of the total mass of the composition; the pour point depressant accounts for 0.05 to 3 percent (preferably 0.1 to 1 percent) of the total mass of the composition; the lubricating base oil constitutes the main component of the composition.
12. A method of making a diesel engine oil composition as claimed in any one of claims 1 to 11, comprising the step of mixing the various additives with a lubricating base oil.
CN201811195381.8A 2018-10-15 2018-10-15 Diesel engine oil composition and preparation method thereof Pending CN111040842A (en)

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CN116042294B (en) * 2021-10-28 2024-05-17 中国石油化工股份有限公司 Lubricating oil composition suitable for diesel engine and preparation method and application thereof
CN116064186A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 Lubricating grease capable of self-warning and preparation method and application thereof

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